Tertiary alkanolamines to reduce ozone fading of dyed polyamide fibers

ABSTRACT

When from about 0.3% to about 8% of tertiary amines formed by the reaction between I (A) diepoxides and/or polyepoxides and (B) secondary amines, or between II (A) diepoxides and (B) ammonia, primary amines, and/or primary tertiary diamines ARE COATED ON NYLON FIBER, OR ARE ADDED TO THE DYEBATH OR ARE COATED ON DYED FIBERS, IMPROVED DYEFASTNESS TO OZONE IS OBTAINED COMPARED TO AN UNTREATED DYED NYLON FIBER.

United States Patent 1191 Lofquist TERTIARY ALKANOLAMINES TO REDUCE OZONE FADING OF DYED POLYAMIDE FIBERS [75] Inventor: Robert Alden Lofquist, Richmond,

[73] Assignee: Allied Chemical Corporation,

Petersburg, Va.

[22] Filed: Oct. 30, 1972 [21] Appl. No.: 302,385

[52] U.S. Cl. 8/165; 8/74; 117/138.8 N; 117/1395 A 51 Int. Cl D06p 5/02 58 Field of Search 8/165, 74; l17/l38.8 N, 117/1395 A [56] References Cited UNITED STATES PATENTS 2,132,074 10/1938 Kartaschoff et a1. 8/74 1451 July 1,1975

3,794,464 2/1974 Lofquist et a1 8/165 Primary ExaminerStephen J. Lechert, Jr. Attorney, Agent, or Firm-Richard A. Anderson [57] ABSTRACT are coated on nylon fiber, or are added to the dyebath or are coated on dyed fibers, improved dyefastness to ozone is obtained compared to an untreated dyed nylon fiber.

2 Claims, No Drawings TERTIARY ALKANOLAMINES TO REDUCE OZONE FADING OF DYED POLYAMIDE FIBERS CROSS-REFERENCE TO RELATED APPLICATION This application is a companion case to an application filed by Robert Alden Lofquist and Peter Reginald Saunders, Ser. No. 302,384, filed on Oct. 30, 1974, even date with this application and herewith incorporated by reference.

BACKGROUND OF THE INVENTION The object of this invention is to reduce or prevent the fading of dyed nylon fabrics caused by the presence of ozone. By fading is meant the decrease in concentration of a dye in the fiber such that the fiber becomes less intensely colored or changes color, for example, dark blue to light blue, or green to yellow, because of the loss of a blue dye.

Ozone is normally present in air at sea level at con centrations of about 1 to parts per hundred million. Despite this extremely low concentration, severe fading caused by ozone has been observed.

Ozone is an allotropic form of oxygen. The molecule of ordinary oxygen consists of two atoms of oxygen whereas the molecule of ozone is formed from three atoms of oxygen. Ozone is created in the upper atmosphere by the action of high energy radiation from the sun splitting oxygen molecules into separate oxygen atoms. The individual atoms then combine with diatomic oxygen molecules (02) to form triatomic ozone (0 This ozone then diffuses down through the atmosphere.

Ozone is a vigorous electrophilic reagent, that is, it acts by sharing electrons which previously belonged exclusively to another molecule (See C. K. lngolds, Structure and Mechanism in Organic Chemistry, Cornell University Press, 1953, page 201 An example of this sharing is the attack of ozone on a carboncarbon double bond to form an ozonide.

When ozone attacks a dye, it can attack at a double bond in the dye or at an amine nitrogen, or other sites where there are electron pairs available. The dyes which are attacked are usually anthraquinone type dyes. Lebensaft, in his doctoral dissertation (University of North Carolina at Greensboro, 1970) stated that ozone attacks the anthraquinone nucleus to form derivatives of phthalic acid.

Disperse type dyes and cationic dyes are those most frequently attacked, but under severe conditions, it is believed that almost all dyes are affected by ozone.

It is believed that the dye diffuses through the fiber to contact the ozone at the surface of the fiber, rather than ozone diffusing through the fiber to a relatively immobile dye. Part of the evidence for this is that any physical treatment to the fiber that increases the mobility of the dye, increases its ozone fading. For this reason, it is felt that any protective agent must also be able to diffuse through the fiber, if it does not form an impenetrable film on the surface of the fiber.

There is some evidence that water molecules must be present in the nylon fiber in order for ozone fading to take place, but whether its action is that of a swelling agent or whether it is involved in a primary or secondary oxidation step is unclear. Lebensaft, cited above, believed it functions principally as a swelling agent and a carrier.

Ozone fading can be decreased by reduction of the specific surface of the yarn. This reduction is undesirable in end-uses that need a bulky yarn. Ozone fading is also diminished by changes in polymer morphology and orientation, but these techniques are inherently expensive.

SUMMARY OF THE INVENTION A method and composition have been found for improving the fastness of dyes when exposed to ozone in polycarbonamide fibers. The method consists of exposing the fibers to ozone in the presence of a compound selected from the group consisting of compounds having at least two groups attached to nitrogen atoms created by (A) the reaction between diepoxides and ammonia, primary alkyl amines, secondary alkyl amines, or primarytertiary alkyl diamines, or (B) created by the reaction between polyepoxides and secondary alkyl amines.

Primary amines mentioned above include alkylamines such as hexylamine, alkanolamines such as ethanolamine or tris-(hydroxymethyl)aminomethane. Diprimary amines include 1,6-hexanediamine, l,3-diamino2-hydroxypropane, m-xylylene-diamine, bis-(2aminoethyl)-sulfide, N,N'-bis-(2aminopropyl)- piperazine, N,N-bis-(3-aminopropyl)methylamine, and polyoxypropyleneamines such as Jeffamine D230, from Jefferson Chemical Co.

Polyprimary amines include NCl999 from Dow Chemical Company, a triamine derived from glycerine.

Secondary amines include dimethylamine, diethanolamine, N-ethylethanolamine and dibenzylamine.

Secondary-secondary diamines include N,N'- dimethylethylenediamine, l,3-di-( 4-piperidyl propane, and piperazine.

Primary-secondary diamines include N-(2-aminoethyl)piperazine, N-(2-hydroxyethyl l ,3-

diaminopropane, aminoethyl-ethanolamine, and N-methyl-1,3-propanediamine.

Primary-tertiary diamines include N,N-

dimethylaminopropylamine, N-(3-aminopropyl)- diethanolamine, N(3-aminopropyl)-piperidine.

Diepoxides include butadiene dioxide, vinyl cyclohexane dioxide; dipentene dioxide, the diglycidyl ether of bisphenol A and diglycidyl ether, and 1,4-butanedioldiglycidyl ether.

olyepoxides include glycidyl ethers of novalaks such as Dows D.E.R. 431; Shells EPON 1031, the tetraglycidyl ether of 1,1,2,2-tetrakis(4-hydroxyphenyl) ethane; and the triglyclydyl ether of 1,3,5- trihydroxybenzene.

The reaction between amines having an NH bond and compounds having the ring creates new compounds having the structure Schechter, Wynstra and Kurkjy reported in Volume 48, No. 1, pages 94-97 of Industrial and Engineering Chemistry that primary amines and phenyl glycidyl ether react together to form B-hydroxy alkylamines almost quantitatively. They found that the reaction between equimolar amounts of phenyl glycidyl ether and diethanolamine was so exothermic that the experiment was uncontrollable, but analysis showed that the epoxide was completely consumed and the theoretical amount of tertiary amine had been formed.

Chapman, Isaacs and Parker in the Journal of the Chemical Society Transactions, volume 195, pp. 1925- reported that the mechanism is a simple, second order, nucleophilic displacement of oxygen by the nitrogen, usually on the carbon with the fewest substit uents, i.e., most hydrogens. They feel it is probably due to steric factors, there being more room for the bulky secondary amine where there are fewer or smaller substituents.

lwakura and Matsuzaki reported in Kobunshi Kagaku, Volume 17, pp. 703-709 1960), that primary amines act as difunctional compounds and primary diamines as tetrafunctional compounds in their reactions with epoxides. They found that diepoxy compounds discoloring the yarn and with little or no effect on the shade of the dyed fiber.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE 1 A 250 ml, 3-necked round-bottom flask was equipped with a condenser, a dropping funnel and a thermometer. The weight of amine listed below was introduced and 100 ml of the solvent listed below. The solution was stirred by means of a magnetic stirrer. The

Table for Example 1 Reaction Amine Solvent 100 ml water la 45 gms (0.4 equiv.)

dimethylamine solution) dimethylamine (40% solution) with primary monoamines and secondary diamines produced linear polymers, soluble in organic solvents.

The reaction between the epoxides and amines does not occur in the absence of polar solvents when the amine compound does not have hydroxyl substituents. For this reason, and to moderate any exotherm, all the reactions listed in the examples were conducted in water or an alcohol. Schecter, Wynstra and Kurkjy, quoted above, found that the hydrogen donor, i.e., the alcohol or water, does not end up as part of the product.

The product of the above reactions or mixtures of the above compounds can be coated on nylon fibers before or after dyeing, or in the dyebath in amounts of from about 0.1 to about 8%, preferably 0.3 to about 4% on the weight of the fiber.

The rate of fading of the dye or dyes, especially disperse or cationic dyes, is substantially reduced by the incorporation or coating of these ,B-hydroxyalkylamine compounds. These compounds are effective without Description of Epoxide Product 28.4 gms (0.4 equiv.) amber solid I .2.7.8-diepoxyoctane 28.0 gms (0.4 equiv.)

vinyleyclohexane dioxide amber viscous liquid 35 gms (0.5 equiv.) amber fluid vinylcyclohexane dioxide 35 gms (0.5 equiv.) light yellow solid l,2,7,8-diepoxyoctane 35 gms (0.5 equiv.) amber liquid vinylcyclohexane dioxide 28.4 gms (0.4 equiv.) amber fluid 1.2.7.8-diepoxyoctane 280 gms (0.4 equiv.)

vinylcyclohexane dioxide amber viscous liquid epoxide was put in the dropping funnel, and added with vigorous stirring at the rate of about three drops per second.

When all the epoxide wasadded, the flask was heated to reflux and the contents refluxed for 1 hour. Then the reflux condenser and the separatory funnel were removed, and the solvent was removed by distillation under vacuum.

In a later example, it will be shown that an exact equivalence of amine and epoxide is not required to achieve good ozone fading protection. One gram of phenol was added to the solvent as a catalyst in reaction lg.

EXAMPLE 2 The following are examples of the reaction between alkylalkanolamines and diepoxides. The apparatus and the technique used to make these materials were the same as those of Example I.

Table for Example 2 Description of Reaction Amine Solvent Epoxide Liquid Product 2a 30 gms (0.4 equiv.) cc water 35.5 gms (0.5 equiv.) light amber viscous 2-( methylamino )ethanol I ,2,7,8-diepoxyoctane 2b 30 gms (0.4 equiv.) 100 cc water 35 gms (0.5 equiv.) amber viscous Z-(methylamino )ethanol vinylcyclohexane dioxide Reaction Amine 30 gms (0.4 equiv.)

2-( methylamino )ethanol Eponite 100 is manufactured by Shell Chemical Z-methylamino )cthunol 100 cc water 100 cc water 100 cc ethanol 100 cc water 100 cc ethanol 100 cc i-propanol 100 cc ethanol Table for Example 2 Solvent Epoxide 28 gms (0.4 equiv.)

vinylcyclohexane dioxide 28.4 gms (0.4 equiv.)

1 ,2,7,8diepoxyoctane 67 gms Eponite 100.

67 gms Eponitc 100 Description of Liquid Product amber viscous amber viscous pale yellow viscous dark viscous pale yellow viscous pale yellow viscous pale yellow viscous pale yellow viscous reaction in Examples 311 and 3j. D.E.R. 332 is pure liq- Company. It is a diepoxide, analyzed at 167 grams per uid diglycidyl ether of bisphenol A, with an epoxy epoxide group. Reactions 2g, 212, and 2i were run to discover whether the solvent had any effect. Reaction 2j was run with one gram phenol to discover whether a phenolic catalyst had any effect on the effectiveness of the product as an antiozonant (See Example 20a).

dialkanolamines and diepoxides. The procedure was EXAMPLE 3 The following are examples of the reaction between the same as in Example l.

Chemical Company.

equivalent weight of 170, made by Dow Chemical Company. ERL 2772 is a low viscosity diglycidyl ether of bisphenol A made by Union Carbide, having an epoxy equivalent weight of 170. D.E.R. 736 is the di- 5 glycidyl ether of tetrapropylene glycol, made by Dow fect of varying the ratio of amine to epoxide.

Table for Example 3 Description of Reaction Amine Solvent Epoxide Liquid Product 3a 42.1 gms (0.4 equiv.) 100 cc water 35.5 gms (0.5 equiv.) yellow-amber viscous diethanolamine 1,2,7,8-diepoxyoctane 3b 42.1 gms (0.4 equiv.) 100 cc water gms (0.5 equiv.) golden viscous diethylanolamine vinylcyclohexane dioxide 3:: 53.3 gms (0.4 vquiv.) 100 cc water 35 gms (0.5 vquiv.) yellow amorphous semi-solid diisopropanolamine vinylcyclohexane dioxide 3d 53.3 gms (0.4 equiv.) 100 cc water 28 gms (0.4 equiv.) yellow amorphous semi-solid diisopropanolamine vinylcyclohexane dioxide Be 42.1 gms (0.4 equiv.) 100 cc ethanol 67 gms (0.4 equiv.) pale yellow viscous diethanolamine Eponite 100 31' 53.3 gms (0.4 vquiv.) 920 cc water 28 gms (0.4 vquiv.) yellow Siscous diisopropanolamine vinylcyclohexane 4ioxide 3g 29k00042gms (0.2 vquiv.) 120 cc ethanol 34 gms (0.2 equiv.) D.E.R. 332 colorless crystalline solid diethanolamine 3h 21 gms (0.2 equiv.) 100 cc ethanol 34 gms (0.2 equiv.) D.E.R. 332 colorless crystalline solid diethanolamine 3i 26.6 gms (0.2 equiv.) 100 cc ethanol 34 gms (0.2 equiv.) D.E.R. 332 colorless crystalline solid diisopropanolamine 3j 26.6 gms (0.2 equiv.) 100 cc ethanol 34 gms (0.2 equiv.) D.E.R. 332 colorless crystalline solid diisopropanolamine 3k 21 gms (0.2 equiv.) 100 cc ethanol 34 gms (0.2 equiv.) ERL 2772 light yellow crystalline solid diethanolamme 3l 21 gms (0.2 equiv.) 100 cc ethanol 27 gms (0.2 equiv.) D.E.R. 736 light yellow viscous diethanolamine 3m 26.3 gms (0.25 equiv.) 100 cc ethanol 27.6 gms (0.162 equiv.) D.E.R. 332 colorless crystalline solid diethanolamine 3n 26.3 gms (0.25 equiv.) 100 cc ethanol 21.2 gms (0.125 equiv.) D.E.R. 332 light yellow crystalline solid diethanolamine 30 21.0 gms (0.20 equiv.) 100 cc ethanol 27.2 gms (0.160 equiv.) D.E.R. 332 colorless crystalline solid diethanolamine One gram of phenol was added to the solvent, as a catalyst for the reaction in Example 3f, 1 gram of sali-' cyclic acid was added to the solvent as a catalyst for the Table for Example 4 EXAMPLE 4 The following are examples of the reaction between secondary amines and polyepoxides.

Description Reaction Amine Solvent Epoxide of Product 4a 16.8 gms (0.15 vquiv.) dimethylamine cc ethanol 43.2 gms (0.15 vquiv.) dark viscous liquid (40% solution) EPON 1031 Table for Example 4(ontinued Description Reaction Amine Solvent Epoxide of Product 4b 15 grns (0.2 equiv.) Z-methylamino) I cc ethanol 35 gms (0.2 equiv.) pale yellow semi-solid ethanol D.E.N. 43l I 4c 21 grns (0.2 equiv.) diethanolamine 100 cc ethanol 57.6 gms (0.2 vquiv.) red-amber lmorphous solid EPON l03l 4d 21 gms (0.2 equiv.) diethanolamine 100 cc ethanol 32.8 gms (0.2 equiv.) pale yellow viscous liquid EPON 812 4c 21 gms (0.2 equiv.) diethanolamine 100cc ethanol 35 gms (0.2 Squiv.) pale qvllow semi-solid D.E.N. 43]

BEN. 43] is Dow Chemical Companys polyglycidyl The product of reaction 4e has a multiplicity of nitroether of phenol-formaldehyde novolak; the weight per gens with three times as many hydroxyls as nitrogens.

epoxide was found to be 175 grams. EPON 1031 is Th Handbook of E oxy Resins by H. Lee and K, made by Shell Chemical; it is the tetraglycidyl ether of Neville, McGraw-Hill Book Company, New York,

tetraphenylethane. Its weight per epoxide was found to 1967, is a useful reference, especially Chapter 5, be 288 grams. EPON 812 is the triglycidyl ether of Epoxy-Resin Curing Mechanism. Chapters 7, 8 and glycerol, manufactured by Shell Chemical Company. It 9 describe primary and secondary amines which can be was analyzed to have an epoxy equivalent weight of reacted with epoxides. Chapter 5 includes a table of 164 grams. commercially available epoxy resins, that is, monoepoxides, diepoxides, and polyepoxides. EXAMPLE 5 The chemicals made by the reactions described The following are examples of the reaction between b e were tested on dyed sleeves, by coating the primary amines and diepoxides. 7S sleeves with the chemicals, exposing the sleeves to Table for Example 5 Description Reaction Amine Solvent Epoxide of Product 5a 20.2 gms (0.4 equiv.) l00 cc water 28.4 gms (0.4 equiv.) 1.2.7.8- light amber semi-solid n-hexylamine diepoxyoctane 5b 15 gms (0.4 equiv.) 100 cc water 28.4 grns (0.4 equiv.) 1.2.7.8- light yellow semi-solid l-amino-Z-propanol diepoxyoctane 5c 21 gms (0.4 equiv.) Z-amino- 100 cc water 28.4 gms (0.4 equiv.) l,2,7.8- colorless amorphous Z-methyl-l .3-propanediol diepoxyoctane solid EXAMPLES 67 ozone and then measuring the loss of color.

Example 6 IS an example of a primary-tertiary di- EXAMPLE 8 amine reacted with diepoxides.

Example 7 is an example of ammonia reacted with a Cationic dyeable polycaprolactam was made having diepoxide. a formic acid relative viscosity (FAV) of about 60, and

Table for Examples 6 and 7 Reaction Example 6 13.02 gms (0.2 vquiv.) N.N-dimethyl- 100 cc ethanol 33.5 gms (0.2 vquiv.) yellow lmorphous l,3-diaminopropane Example 7 7.6 cc of 0% MMONlA (0.33 vquiv.) l00 cc ethanol 67 gms (0.2 vquiv.) viscous light 8ellow Eponite I00 liquid The molecules in the above reactions vary from two containing about 90 equivalents of sulfonate pendant nitrogens and two hydroxyls as with the product of reto the polymerchain, the sulfonates being provided by action la: the introduction of 5-sulfoisophthalic acid sodium salt OH OH to the monomer prior to polymerization. The polymer had about 80 gram'equivalents of carboxyls and about 14C11 CHCH CH CH CH Cl-ICH N(C11 20 gram-equivalents of amines per lO grams of polymer. The polymer was spun at 280 C., plied, drawn at to two nitrogens and four hydroxyls as with the product a draw ratio of 31.0, crimped and then chopped into of reaction 2a: 7-inch lengths, carded and spun into staple yarn with a CH H 3 3 HOCH Cii NCil CHOIICI-I CH CH CH CH CHOHCH2NCH2CH OH to two nitrogens and six hydroxyls as with the product cotton count of 2.0. Each filament of the yarn had a Y- of reaction 3g: cross section with a 3.2 modification ratio. The yarns (3H3 (HOCH CH NCH CHOHCH OOCOOCH CHOHCH N (CI-I CH OH) 2 were knitted into sleeves, and then dyed to a moss green in a dyebath, containing 0.3 percent (O.W.F) Sevron Yellow 8 GMF, 0.25% Astrazon Blue 3RL (C.l. Basic Blue 47), 2% Hypochem PNDl l, 1% Hypochem and about 17 gram-equivalents of amines per 10 grams of polymer. The polymer was spun, plied, drawn, chopped into staple, carded and spun into staple yarn and autoclaved by steaming in an autoclave at 230C.

CDL-60, and enough monoand/or disodium phos-. 5 for 5 minutes, followed by 3 ten-minute cycles of steam phate to adjust the pH to neutral. treatment at 260F. This steam treatment is used to The sleeves were cut into 5-inch long segments, simulate the twist setting that such yarns receive when weighed, and then soaked in ethanol solutions of the they are used in shag carpets, for example. following reaction products for 20 minutes. The sec' The autoclaved yarns were dyed Olive 1 whose dyetions of sleeve were then dried in the air for about sixbath recipe is described in Example 1 1. teen hours, weighed to determine the pickup of the re- The dyed yarns were coated with solutions of the action product and then exposed to three cycles of 80 Chemicals given below, and tested, and the fading W85 pphm ozone at 104F., and a relative humidity of at measured in the same manner as described in Example least 95%. 11.

The solutions, the amount of coating and the result The solutions, the amount of coating and the results of 3 cycles of ozone exposure are listed below: of 3 cycles of ozone exposure was listed below:

r/r Pi k p 3E Solution in 200 ml ethanol /rPickup AE a) Control in 200 ml ethanol 0 10.7 a) 1 gm product of reaction 10 1.9 1.8 Product f reaction l rg ly 1. 1. h) 2 gfllS product of reaction 10 3.1 4.7 (CH3)2N'CH2CHOH c) 1 gm product of reaction 3a 1.6 4.2 (CH2)4CHOHCH2N(CH3)2 d) 2 gms product of reaction 32: 2.7 .6 e) 4 gms product of reaction 3a 5.1 2.8 f) 1 gm product of reaction 1d 1.1 7.0 I g) 2 gms product of reaction 1d 2.4 .9 A cycle is that amount of exposure which occurs h)4gms produgtofreaction 1d 4.o 4.6 when a nylon control fabric shows a specified color )cmtmllust'oo mlethaml O change as measured by a colorimeter.

The control fabric is a nylon sleeve dyed Olive 1, a tertiary shade given by a dyebath containing 0.69% (O.W.F.) Disperse Blue 3, (such as Celliton Blue EXAMPLE 1() FFRN), 0.080770 (O.W.F.) Celliton Pink RF, and PQ Yellow Dlsperse Blue Sleeves from the same yarn as described in Example 3 y especlally sepsltlve to 8 but autoclaved at 260F. as described in Example 9 The degree of fadlng after expo r to ozone was were cut into sections, soaked in the following solutions measured on a Hunter Color Difference Meter. The d h exposed to 3 Cydes f Ozone using h hmeasurement is given in terms of AE units, a smaller AE Qdg d ib d i Exam le 8, being associated with less fading.

AE is calculated from the differences between the L, a and b readings before the yarn is exposed to ozone, 4O

S l t 200 1 th' 1 7 P' k AE and the L, a, and b readings after the yarn 1S exposed m m e m up to ozone, using the equations: a) 0.8 gm product of reaction le 0,15 10,4 b) 1.5 gms product of reaction 1c 1.9 7.6 AB: V (ALF-H A +(Ab) c) 3.0 gms product of reaction 1e 3.2 1.7 d) 0.8 gm product of reaction 2a 0.64 4.2 L is a 0100 reading of black to white; a measures e) 15 gms Pmduct ofreicilon f) 3.0 gms product of reaction 2a 3.7 1.0 redness to greenness; and b measures yellowness to gH-USIZOO methanol 0 341 blucness.

The Hunter Color Difference Meter is believed to measure color, as seen in average daylight, in a manner th wa in whi h h h mane eres onds to similar to e y c t e u y p EXAMPLE H color. Experimentation has shown that the eye can match y Color a combmauon of three pnmai Sleeves from the same yarn as described in Example fg d i g d f i g y Th 8, except that it was autoclaved at 280F. prior to dye- Spec 1e y a t lmenslona g d b ing, were cut into sections, soaked in the following so- Color P'fference g ff? meisures t 6 lg i lutions, and then exposed to three cycles of ozone using a specimen throug iterst at correspon tot et ree the methods described in Example 8 primary lights. The measurements made, therefore, correspond to the way the average human eye responds to light, as these responses are set forth in the CIE Standard Observer. The Standard Observer is a 50mm m 200 m1 elhanol PlCkuP AE table of values derived from experiments with human 3) 1 gm product of Eamon 3C 104 141 observers, and recommended for use in 1931 by the lnb) i gm pl'OdAJCI Offreaction 2211b 4 ,5 r c) gms pro ucto reaction 2.3 ternational Commission on Illumination. d) 1 gm product of reaction 1a 21 35 e) 2 gms product of reaction la 3.6 5.2 EXAMPLE 9 f) 1 gm product of reaction 3d 1.4 8.6 g) 2 gms product of reaction 3d 2.5 5.2 Light dyeing polycaprolactam was made having a forh) 1 gm product of reaction 26 L6 mic acid relative viscosity (FAV) of about 67. The l Zgms 9 of ream'on 2c 27 J) Control, ust 200 ml ethanol 0 34.8

polymer had about gram-equivalents of carboxyls EXAMPLE l2 S I t' 200 1 thz l 7 Picku AE Sleeves identical to those of Example 11 were cut m m c I p into sections, soaked in the following solutions and a) 1 gm product f m x 1,3 10,6 then exposed to ozone using the methods of Example 11) 2 gm Product of rwqmm 8 l 5 c) 1 gm product of reaction 1g 1.7 5.2 d) 2 gms product of reaction 1g 3.2 2.6 e) Control. just 200 ml ethanol 0 23.9

Solution in 200 ml ethanol Pickup AE u) 1 gm product of reaction 3b 21 6.6 EXAMPLE 17 2 3 3. 2. 2 ygfilfififlgfgigjiflgT ,3 g Sleeves identical to those of Example 10 were treated d) 3 gm PmduCt 0f reaction 3d except that they were autoclaved at 270F. The sleeves 7 f 6' were cut into sections, soaked in the following solutions, and then exposed to ozone as in Example 8.

EXAMPLE 13 S1t"2001th-l 7P'k AE Sleeves identical to those of Example 10 were cut m m e I m up into sections. soaked in the following solutions and a) 1 gm productof reaction g 3,3 1 h) 1 gm product of reaction 3f 2.5 3.3 then exposed to ozone usmg the method of Example 8 c) 1 gm product of reaction 3g 19 38 d) 1 gm product of reaction 3h 1.5 4.1 e) 1 gm product of reaction 3i 2.2 3.4 f) 1 gm product of reaction 3j 1.5 5.2 g) Control. just 200 ml ethanol 0 26.7 Solution in 200 ml ethanol 7: Pickup AE a) 1 gm product of reaction 3e 1.4 3.3 b) 2 gms product of reaction 3e 2.7 3.3 c) 1 gm product of reaction 2e 1.6 4.8 d) 2 gms product of reaction 2e 1.8 2.1 EXAMPLE [8 v n e) controljust'oo ml etham] O Sleeves identical to those of Example 17 were cut into sections, soaked in the following solutions, and then exposed to ozone as in Example 8.

EXAMPLE 14 Sleeves identical to those of Example 10 were cut into sections, soaked in the following solutions, and 200 ml ethanol Pickup AE then exposed to ozone using the method of Example 8. a) 1 gm product of reaction 3k 17 19 b) 1 gm product of reaction 31 2.0 2.9 c) 1 gm product of reaction 4c 0.8 3.6 40 d) 1 gm product of reaction 4d 2.1 1.7 e) Control, just 200 ml ethanol 0 27.1

Solution in 200 ml ethanol '7! Pickup AE a) 1 gm product of reaction 1c 1.1 4.8 b) 2 gms product of reaction 1c 2.0 2.9 c) Control. just 200 m1 of ethanol 0 20.4 EXAMPLE 19 Sleeves identical to those of Example 10 were cut into sections, soaked in the following solutions, and EXAMP 15 then exposed to ozone, as in Example 8.

Sleeves identical to those of Example 10 were cut into sections, soaked in the following solutions and then were exposed to ozone as in Example 8. Solution "1300 ethanol 7! Pickup A5 a) 1 gm product of reaction 4a 0.5 4.2

b) 1 gm product of reaction 2g 1.3 1.4

c) 1 gm product of reaction 2f 1.3 2.8

SOlUllOI'l 111 200 m1 ethanol 7! Pickup AE d) 1 gm product of reaction 4 L2 3 6 e) 1 gm product of reaction 4b 1.2 1.8 a) 1 gm product of reaction 6a 1.3 3.5 f) 1 gm product of reaction 2h 1.3 1.7 b) 2 gms product of reaction 6a 2.9 3.8 g) 1 gm product of reaction 2i 1.4 1.6 c) 1 gm product of reaction 6b 1.5 4.8 h) Control, just 200 ml ethanol 0 21.5 d) 2 gms product of reaction 6b 2.6 3.4 e) 1 gm product of reaction 7c 1.5 7.5 f) 2 gms product of reaction 7c 3.0 4.8 g) Control. just 200 m1 ethanol 0 23.9

EXAMPLE 20 Sleeves identical to those of Exam 1e 9 were cut int EXAMPLE 16 p 0 sections, soaked in the following solutions, and then exposed to ozone, as in Example 8. The results are listed below.

Sleeves identical to those of Example 10 were treated as in Example 8 after soaking in the following solutions.

Solution in 200 ml ethanol '4 Picku AE i n in 2 ml ethanol 7: Pickup AE a) 1 gm product of reaction 1f 1.8 3.2 1 g p f of reaction 6 L9 5.5 b) 1 gm product f reaction 2 1 7 39 b) Control. ust 20 ml ethanol 0 27.0 c) 1 gm product of reaction 30 1.4 10.6 5 d) 1 gm product of reaction la 1.4 4.7 e) 1 gm product of reaction 2c [.0 5.9 f) 1 gm product of reaction 3e 0.8 9.2 g) 2 gm product of reaction 3e 2.6 5.5 EXAMPLE 23 Control J 200 ml ethanol 0 The procedure of Example 1 l was repeated but using cationic dyeable nylon 6,6 staple (Du Pont T367) instead of cationic dyeable polycaprolactam. The antiozonants used, the amount of pickup of the antiozonant and the result of 3 cycles of ozone exposure are listed EXAMPLE 2] below; Sleeves identical to those of Example 17 were cut into sections, soaked in the following solutions and Solution In 200 II album PIckup AE then exposed to ozone as in Example 8. The coatlngs and the results of exposure are listed below. Control. soaked in 200 ml ethanol 0 4.2 a) 0.8 gm product of reaction 2a 1.] 20 b) 1 gm product of reaction 3d l l L5 c) 1 gm product of reaction 5b 0.6 Solution in 200 ml ethanol '7: Pickup AE a) 0.8 gm product of reaction 3g 1.18 l0.4 b) l.2 gms product of reaction 3g [.78 5.7 I claim: 0) 2.0 gms product of reaction 3g 2.85 4.5 a d 0.8 gm product of reaction 3 Q95 5 1. A composition of matter comprising from about 92 12 g Productof reaction 3m to about 99.9% by weight of a polycarbonamide and f) 2.0 grns product of reaction 3m 2.78 8.2 g) 0.8 gm product of reaction 3n 8.9 from about 0.1 to about 8% by weight of a compound h) g Product Of reaction 3n 10x3 coated on said polycarbonamide selected from the 1) 2.0 gms product of reaction 3n 3.04 4.5 0.8 gm pIOdIICt of reaction I08 92 group consisting of compounds having at least two 1.2 grns product of reaction 30 1.77 5.7 30 I I l) 2.0 gms product of reaction 30 2.95 10.4 C C O1.I- 111) Control. just 200 ml ethanol 0 30.0 I I groups attached to nitrogen atoms and created by the reaction of A. a polyepoxide with a secondary alkyl amine,

. m mine a d- EXAMPLE 22 B a diepoxide with a primary alkyl onoa I n /or ammonia and/or a secondary alkyl amine. Sleeves identical to those of Example 17 were cut The composition f daim 1 wherein said into sleeves, soaked in the following solutions and then pound is Created by the reaction of a diepoxide with a exposed to ozone as in Example 8. The coatings and the 40 secondary alkyl amine results of exposure are listed below. 

1. A COMPOSITION OF MATTER COMPRISING FROM ABOUT 92 TO ABOUT 99.9% BY WEIGHT OF A POLYCARBONAMIDE AND FROM ABOUT 0.1 TO ABOUT 8% BY WEIGHT OF A COMPOUND COATED ON SAID POLYCARBONAMIDE SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING AT LEAST TWO
 2. The composition of claim 1 wherein said compound is created by the reaction of a diepoxide with a secondary alkyl amine. 